CN108963230B - Process for preparing sodium-sulfur all-solid-state battery composite positive electrode material and battery - Google Patents
Process for preparing sodium-sulfur all-solid-state battery composite positive electrode material and battery Download PDFInfo
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- CN108963230B CN108963230B CN201810809652.8A CN201810809652A CN108963230B CN 108963230 B CN108963230 B CN 108963230B CN 201810809652 A CN201810809652 A CN 201810809652A CN 108963230 B CN108963230 B CN 108963230B
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Abstract
The invention discloses a process for preparing a sodium-sulfur all-solid-state battery composite anode material and a battery, wherein composite electrode strips with different thicknesses and widths are obtained by adjusting parameters such as melting temperature, driving gas pressure, copper roller rotating speed, crucible aperture and the like, so that the process is widely applied to the solid-state battery, when the composite electrode material is prepared by adopting a melt spinning process, various required elements can be alloyed or multi-component is uniformly melted in the melting process, and the melt spinning process is as high as 104The cooling speed of the temperature/s can realize rapid quenching solidification, and a microcrystalline or even amorphous composite strip is obtained, and the particle size of each component is smaller, so that the reaction kinetics of the material in the charging and discharging process is improved, the interface action is improved, and the mechanical property of the electrode is also improved.
Description
Technical Field
The invention relates to the technical field of solid-state batteries, in particular to a process for preparing a sodium-sulfur all-solid-state battery composite positive electrode material and a battery.
Background
Sodium ion all-solid-state batteries have recently received increasing attention due to their abundant storage, high safety, and promising high energy density, long cycle life batteries, etc. Due to the intrinsic characteristics of solid electrolytes, the development of new composite electrode materials, including sodium-storage alloy negative electrode materials, sodium/lithium-sulfur battery composite positive electrodes, and the like, and the solution of the problem of contact between the solid electrolyte and the electrode interface become more and more important compared with the conventional liquid batteries. The sodium-sulfur composite positive electrode material is mostly prepared by ball milling and cold pressing, all components are physically mixed, and the electrode prepared by the high-pressure cold pressing mode is easy to generate stress concentration, so that in the use process of a subsequent assembled battery, the stress concentration is further caused by the change of the volume, the material crushing and other consequences are finally caused, the interface contact between the electrode and the solid electrolyte is influenced, and the rapid decline of the cycle performance of the battery is caused. Based on the advantages of the application of the novel composite electrode in the solid-state battery and the defects of the existing composite electrode preparation process, the development of the novel composite electrode material preparation process is concerned more and more by people, so that the novel composite electrode material can meet various requirements of the solid-state battery on the electrode material. Therefore, a process for preparing the sodium-sulfur all-solid-state battery composite positive electrode material and a battery are provided.
Disclosure of Invention
The invention mainly aims to provide a process for preparing a sodium-sulfur all-solid-state battery composite positive electrode material and a battery, which can effectively solve the problems in the background technology.
In order to achieve the purpose, the invention adopts the technical scheme that:
a process for preparing a sodium-sulfur all-solid-state battery composite positive electrode material comprises the following steps:
the method comprises the following steps: taking original Na2S, P2S5 and CMK-3 powder according to the weight ratio of 58-62:9-13: 28-32;
step two: drying the raw materials in the step one, and then putting the dried raw materials into a ball mill for uniform ball milling and mixing;
step three: pressing the raw materials mixed in the step two into blocks, putting the blocks into a crucible of a melt-spun furnace, vacuumizing, introducing inert atmosphere, heating to melt, driving the melt to be sprayed out from an opening at the bottom of the crucible by using air pressure after melting, and dropping the melt onto a copper roller rotating at a high speed, cooling to obtain a composite anode material strip of Na2S-Na3PS4-CMK3 components with micro-nano structure sizes;
step four: and (4) carrying out heat treatment on the strip obtained in the third step to obtain the Na2S-Na3PS4-CMK3 component composite cathode material.
Further, the raw material Na2S in the step one is as follows: P2S 5: the CMK-3 comprises the following components in parts by weight 59.5: 10.5:30.
Further, the ball mill in the second step is a planetary ball mill.
Further, the melting temperature in the third step is 800-.
Furthermore, the size of the opening at the bottom of the crucible in the third step is 2-3 mm.
Further, the heat treatment temperature in the fourth step is 200-300 ℃.
Further, the cooling speed of the copper roller in the third step is 104℃/s。
Further, a sodium-sulfur all-solid battery composite positive electrode battery of the present invention for achieving the above object, the battery positive electrode being equipped with a positive electrode material containing the above-mentioned electrode material.
Compared with the prior art, the invention has the following beneficial effects:
1. the method can prepare composite electrode materials with various alloy components or multiple components, and composite electrode strips with different thicknesses and widths can be obtained by adjusting parameters such as melting temperature, driving gas pressure, copper roller rotating speed, crucible aperture and the like in the melt spinning process, so that the process is more widely applied to solid-state batteries;
2. when the melt spinning process is adopted to prepare the composite electrode material, various required elements can be alloyed or multi-component is uniformly melted in the melting process, and the melt spinning process is as high as 104The cooling speed of DEG C/s can realize rapid quenching solidification to obtain microcrystalline and even amorphous composite strips, and the particle size of each component is smaller, so that the reaction kinetics of the materials in the charging and discharging processes are improved, the interface action is improved, and the mechanical property of the electrode is also improved;
3. in the melting-solidification strip-spinning process of the raw materials, a second-phase dispersed phase is easier to form, so that the mechanical property of the composite electrode material prepared by the strip-spinning method is greatly improved compared with that of the traditional anode material;
4. in the melting-solidification melt-spinning process of raw materials, a buffer material, a solid electrolyte and even an active substance are easy to generate in situ, effective sodium ion and electron transmission channels in the electrode can be improved, the interface contact between the electrode and the solid electrolyte is improved, and compared with the traditional preparation methods such as cold pressing compounding, the composite electrode material prepared by the melt-spinning method does not have the adverse effect of stress concentration caused by the cold pressing compounding process, and the mechanical property of the electrode and the cycle performance of a battery are improved.
In summary, the invention provides a relatively universal method for preparing a composite electrode material for a solid-state battery, and the method adopts a melt-spinning method to prepare the composite electrode material for the solid-state battery, can be used for preparing a composite positive electrode of a sodium-sulfur battery and the like, and is used in the preparation process of an all-solid-state sodium-ion battery.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
The first embodiment is as follows:
a process for preparing a sodium-sulfur all-solid-state battery composite positive electrode material comprises the following steps:
the method comprises the following steps: taking Na2S, P2S5 and CMK-3 powder as raw materials in a weight ratio of 58:9: 28;
step two: and (3) drying the raw materials in the step one, then putting the dried raw materials into a planetary ball mill for uniform ball milling and mixing, and carrying out the whole process under the protection of the atmosphere of a glove box.
Step three: pressing the mixed raw materials into blocks, then putting the blocks into a crucible of a small-sized melt-spun furnace, vacuumizing the crucible, introducing inert atmosphere, heating the blocks to about 800 ℃, observing the melting condition, ejecting the melt from a small hole 2mm in the bottom of the crucible by utilizing air pressure after melting, dropping the melt onto a copper roller rotating at high speed to realize rapid cooling, and generating Na3SP4 solid electrolyte components in the melting process to obtain the composite anode material strip of Na2S-Na3PS4-CMK3 components with micro-nano structure size.
Step four: the composite cathode material strip is subjected to heat treatment at 200 ℃, Na2S is generated in situ from Na3PS4 in the process, the Na2S-Na3PS4-CMK3 component composite cathode material is obtained, and an ion transmission channel between a solid electrolyte and an electrode active material, better interaction and interface contact performance of the solid electrolyte and the electrode active material are ensured.
Example two:
a process for preparing a sodium-sulfur all-solid-state battery composite positive electrode material comprises the following steps:
the method comprises the following steps: taking Na2S, P2S5 and CMK-3 powder as raw materials in a weight ratio of 62:13: 32;
step two: and (3) drying the raw materials in the step one, then putting the dried raw materials into a planetary ball mill for uniform ball milling and mixing, and carrying out the whole process under the protection of the atmosphere of a glove box.
Step three: pressing the mixed raw materials into blocks, then putting the blocks into a crucible of a small-sized melt-spun furnace, vacuumizing the crucible, introducing inert atmosphere, heating the blocks to about 1000 ℃, observing the melting condition, ejecting the melt from a small hole with the diameter of 3mm at the bottom of the crucible by utilizing air pressure after melting, dropping the melt onto a copper roller rotating at high speed to realize rapid cooling, generating Na3SP4 solid electrolyte components in the melting process, and obtaining the composite anode material strip with the components of Na2S-Na3PS4-CMK3 and the size of a micro-nano structure.
Step four: the composite cathode material strip is subjected to heat treatment at 300 ℃, Na2S is generated in situ from Na3PS4 in the process, the Na2S-Na3PS4-CMK3 component composite cathode material is obtained, and an ion transmission channel between a solid electrolyte and an electrode active material, better interaction and interface contact performance of the solid electrolyte and the electrode active material are ensured.
Example three:
a process for preparing a sodium-sulfur all-solid-state battery composite positive electrode material comprises the following steps:
the method comprises the following steps: taking Na2S, P2S5 and CMK-3 powder as raw materials, and mixing the raw materials in parts by weight of 59.5: 10.5: 30;
step two: and (3) drying the raw materials in the step one, then putting the dried raw materials into a planetary ball mill for uniform ball milling and mixing, and carrying out the whole process under the protection of the atmosphere of a glove box.
Step three: pressing the mixed raw materials into blocks, then putting the blocks into a crucible of a small-sized melt-spun furnace, vacuumizing the crucible, introducing inert atmosphere, heating the blocks to about 800 ℃, observing the melting condition, ejecting the melt from a small hole with the diameter of 3mm at the bottom of the crucible by utilizing air pressure after melting, dropping the melt onto a copper roller rotating at high speed to realize rapid cooling, generating Na3SP4 solid electrolyte components in the melting process, and obtaining the composite anode material strip with the components of Na2S-Na3PS4-CMK3 and the size of a micro-nano structure.
Step four: the composite cathode material strip is subjected to heat treatment at 200 ℃, Na2S is generated in situ from Na3PS4 in the process, the Na2S-Na3PS4-CMK3 component composite cathode material is obtained, and an ion transmission channel between a solid electrolyte and an electrode active material, better interaction and interface contact performance of the solid electrolyte and the electrode active material are ensured.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention by those skilled in the art should fall within the protection scope of the present invention without departing from the design spirit of the present invention.
Claims (9)
1. A process for preparing a sodium-sulfur all-solid-state battery composite positive electrode material is characterized by comprising the following steps of:
the method comprises the following steps: taking Na2S, P2S5 and CMK-3 powder as raw materials in a weight ratio of 58-62:9-13: 28-32;
step two: drying the raw materials in the step one, and then putting the dried raw materials into a ball mill for uniform ball milling and mixing;
step three: pressing the raw materials mixed in the step two into blocks, putting the blocks into a crucible of a melt-spun furnace, vacuumizing, introducing inert atmosphere, heating to melt, driving the melt to be sprayed out from an opening at the bottom of the crucible by using air pressure after melting, and dropping the melt onto a copper roller rotating at a high speed, cooling to obtain a composite anode material strip of Na2S-Na3PS4-CMK3 components with micro-nano structure sizes;
step four: and (4) carrying out heat treatment on the strip obtained in the third step to obtain the Na2S-Na3PS4-CMK3 component composite cathode material.
2. The process for preparing the sodium-sulfur all-solid-state battery composite positive electrode material according to claim 1, characterized in that: raw material Na2S in the step one: P2S 5: the CMK-3 comprises the following components in parts by weight 59.5: 10.5:30.
3. The process for preparing the sodium-sulfur all-solid-state battery composite positive electrode material according to claim 1, characterized in that: and the ball mill in the second step is a planetary ball mill.
4. The process for preparing the sodium-sulfur all-solid-state battery composite positive electrode material according to claim 1, characterized in that: the melting temperature in the third step is 800-.
5. The process for preparing the sodium-sulfur all-solid-state battery composite positive electrode material according to claim 1, characterized in that: and in the third step, the opening at the bottom of the crucible is 2-3mm in size.
6. The process for preparing the sodium-sulfur all-solid-state battery composite positive electrode material according to claim 1, characterized in that: the heat treatment temperature in the fourth step is 200-300 ℃.
7. The process for preparing the sodium-sulfur all-solid-state battery composite positive electrode material according to claim 1, characterized in that: the cooling speed of the copper roller in the third step is 104℃/s。
8. The composite positive electrode of the sodium-sulfur all-solid-state battery is characterized by being prepared from the composite positive electrode material of the sodium-sulfur all-solid-state battery prepared by the process of any one of claims 1 to 7.
9. A sodium-sulfur all-solid battery comprising the sodium-sulfur all-solid battery composite positive electrode defined in claim 8.
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| WO2019178533A1 (en) * | 2018-03-16 | 2019-09-19 | University Of Maryland, College Park | All solid-state sodium-sulfur or lithium-sulfur battery prepared using cast-annealing method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1875506A (en) * | 2003-10-31 | 2006-12-06 | 丰田自动车株式会社 | Electroactive material and use thereof |
| CN105470505A (en) * | 2011-07-26 | 2016-04-06 | 公立大学法人大阪府立大学 | All-solid-state secondary cell |
| CN105765778A (en) * | 2013-10-03 | 2016-07-13 | 国立研究开发法人科学技术振兴机构 | Solution for forming layer that contains solid electrolyte for all-solid-state alkali metal secondary batteries, coated active material particles, electrode, all-solid-state alkali metal secondary battery and method for manufacturing same |
| WO2017102011A1 (en) * | 2015-12-17 | 2017-06-22 | Toyota Motor Europe | All-solid-state battery using sodium ion intercalation cathode with li/na exchanging layer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20150364787A1 (en) * | 2011-12-06 | 2015-12-17 | Hui Zhang | Composite Electrolytes for Low Temperature Sodium Batteries |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1875506A (en) * | 2003-10-31 | 2006-12-06 | 丰田自动车株式会社 | Electroactive material and use thereof |
| CN105470505A (en) * | 2011-07-26 | 2016-04-06 | 公立大学法人大阪府立大学 | All-solid-state secondary cell |
| CN105765778A (en) * | 2013-10-03 | 2016-07-13 | 国立研究开发法人科学技术振兴机构 | Solution for forming layer that contains solid electrolyte for all-solid-state alkali metal secondary batteries, coated active material particles, electrode, all-solid-state alkali metal secondary battery and method for manufacturing same |
| WO2017102011A1 (en) * | 2015-12-17 | 2017-06-22 | Toyota Motor Europe | All-solid-state battery using sodium ion intercalation cathode with li/na exchanging layer |
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